US6416696B1 - Aqueous mixed pMDI/phenolic resin binders for the production of wood composite products - Google Patents
Aqueous mixed pMDI/phenolic resin binders for the production of wood composite products Download PDFInfo
- Publication number
- US6416696B1 US6416696B1 US09/465,279 US46527999A US6416696B1 US 6416696 B1 US6416696 B1 US 6416696B1 US 46527999 A US46527999 A US 46527999A US 6416696 B1 US6416696 B1 US 6416696B1
- Authority
- US
- United States
- Prior art keywords
- weight
- component
- isomer
- content
- group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000002023 wood Substances 0.000 title claims abstract description 38
- 229920001568 phenolic resin Polymers 0.000 title claims abstract description 31
- 239000005011 phenolic resin Substances 0.000 title claims abstract description 25
- 239000002131 composite material Substances 0.000 title claims abstract description 23
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 10
- 239000011230 binding agent Substances 0.000 title abstract description 50
- 239000000203 mixture Substances 0.000 claims abstract description 74
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 55
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 54
- 238000000034 method Methods 0.000 claims abstract description 47
- 239000002245 particle Substances 0.000 claims abstract description 19
- 239000007864 aqueous solution Substances 0.000 claims abstract description 15
- 239000006185 dispersion Substances 0.000 claims abstract description 9
- 238000000465 moulding Methods 0.000 claims abstract description 6
- -1 polymethylene Polymers 0.000 claims description 55
- 229920003987 resole Polymers 0.000 claims description 28
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Natural products OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- 239000007787 solid Substances 0.000 claims description 17
- 150000001875 compounds Chemical class 0.000 claims description 16
- 125000004432 carbon atom Chemical group C* 0.000 claims description 14
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 13
- 239000000178 monomer Substances 0.000 claims description 12
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- ORIHZIZPTZTNCU-VMPITWQZSA-N 2-[(E)-hydroxyiminomethyl]phenol Chemical compound O\N=C\C1=CC=CC=C1O ORIHZIZPTZTNCU-VMPITWQZSA-N 0.000 claims description 3
- IIEZCGOWIADGFY-VMPITWQZSA-N 3-[(e)-hydroxyiminomethyl]phenol Chemical compound O\N=C\C1=CC=CC(O)=C1 IIEZCGOWIADGFY-VMPITWQZSA-N 0.000 claims description 3
- LAKIRRXYHHGTBY-UHFFFAOYSA-N 4-[N-hydroxy-C-(4-hydroxyphenyl)carbonimidoyl]phenol Chemical compound C=1C=C(O)C=CC=1C(=NO)C1=CC=C(O)C=C1 LAKIRRXYHHGTBY-UHFFFAOYSA-N 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- LJEARAFLOCEYHX-VMPITWQZSA-N chembl202611 Chemical compound O\N=C\C1=CC=C(O)C=C1 LJEARAFLOCEYHX-VMPITWQZSA-N 0.000 claims description 3
- 125000004464 hydroxyphenyl group Chemical group 0.000 claims description 3
- GVTQQXMVSYYNCC-UHFFFAOYSA-N n-[(2-dodecoxyphenyl)methylidene]hydroxylamine Chemical compound CCCCCCCCCCCCOC1=CC=CC=C1C=NO GVTQQXMVSYYNCC-UHFFFAOYSA-N 0.000 claims description 3
- ZIAIEWWHOFJMLP-UHFFFAOYSA-N n-[(2-heptoxyphenyl)methylidene]hydroxylamine Chemical compound CCCCCCCOC1=CC=CC=C1C=NO ZIAIEWWHOFJMLP-UHFFFAOYSA-N 0.000 claims description 3
- YHEKLJFCDOLGDD-UHFFFAOYSA-N n-[(2-nonoxyphenyl)methylidene]hydroxylamine Chemical compound CCCCCCCCCOC1=CC=CC=C1C=NO YHEKLJFCDOLGDD-UHFFFAOYSA-N 0.000 claims description 3
- 239000012948 isocyanate Substances 0.000 description 35
- 150000002513 isocyanates Chemical class 0.000 description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 34
- 229920005989 resin Polymers 0.000 description 24
- 239000011347 resin Substances 0.000 description 24
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 18
- 239000000047 product Substances 0.000 description 18
- 239000002981 blocking agent Substances 0.000 description 17
- 239000000463 material Substances 0.000 description 17
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 16
- 150000002989 phenols Chemical class 0.000 description 14
- 150000001299 aldehydes Chemical class 0.000 description 11
- 239000003054 catalyst Substances 0.000 description 10
- 238000002156 mixing Methods 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 238000009472 formulation Methods 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 0 *C.*C.*C.*C(=NO)c1ccc(O)cc1.*C(=NO)c1cccc(O)c1.*C(=NO)c1ccccc1O Chemical compound *C.*C.*C.*C(=NO)c1ccc(O)cc1.*C(=NO)c1cccc(O)c1.*C(=NO)c1ccccc1O 0.000 description 6
- 239000002585 base Substances 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000012978 lignocellulosic material Substances 0.000 description 5
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 230000000903 blocking effect Effects 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 150000002923 oximes Chemical class 0.000 description 4
- 239000004814 polyurethane Substances 0.000 description 4
- 229920002635 polyurethane Polymers 0.000 description 4
- 238000003825 pressing Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Natural products C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 3
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 3
- 241000183024 Populus tremula Species 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 229920001807 Urea-formaldehyde Polymers 0.000 description 3
- 239000011149 active material Substances 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- 235000014633 carbohydrates Nutrition 0.000 description 3
- 150000001720 carbohydrates Chemical class 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 230000003472 neutralizing effect Effects 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- 235000012431 wafers Nutrition 0.000 description 3
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 description 2
- VTCDZPUMZAZMSB-UHFFFAOYSA-N 3,4,5-trimethoxyphenol Chemical compound COC1=CC(O)=CC(OC)=C1OC VTCDZPUMZAZMSB-UHFFFAOYSA-N 0.000 description 2
- YCOXTKKNXUZSKD-UHFFFAOYSA-N 3,4-xylenol Chemical compound CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 description 2
- XQDNFAMOIPNVES-UHFFFAOYSA-N 3,5-Dimethoxyphenol Chemical compound COC1=CC(O)=CC(OC)=C1 XQDNFAMOIPNVES-UHFFFAOYSA-N 0.000 description 2
- TUAMRELNJMMDMT-UHFFFAOYSA-N 3,5-xylenol Chemical compound CC1=CC(C)=CC(O)=C1 TUAMRELNJMMDMT-UHFFFAOYSA-N 0.000 description 2
- HMNKTRSOROOSPP-UHFFFAOYSA-N 3-Ethylphenol Chemical compound CCC1=CC=CC(O)=C1 HMNKTRSOROOSPP-UHFFFAOYSA-N 0.000 description 2
- IAVREABSGIHHMO-UHFFFAOYSA-N 3-hydroxybenzaldehyde Chemical compound OC1=CC=CC(C=O)=C1 IAVREABSGIHHMO-UHFFFAOYSA-N 0.000 description 2
- RXNYJUSEXLAVNQ-UHFFFAOYSA-N 4,4'-Dihydroxybenzophenone Chemical compound C1=CC(O)=CC=C1C(=O)C1=CC=C(O)C=C1 RXNYJUSEXLAVNQ-UHFFFAOYSA-N 0.000 description 2
- LJEARAFLOCEYHX-UHFFFAOYSA-N 4-(hydroxyiminomethyl)phenol Chemical compound ON=CC1=CC=C(O)C=C1 LJEARAFLOCEYHX-UHFFFAOYSA-N 0.000 description 2
- MBGGFXOXUIDRJD-UHFFFAOYSA-N 4-Butoxyphenol Chemical compound CCCCOC1=CC=C(O)C=C1 MBGGFXOXUIDRJD-UHFFFAOYSA-N 0.000 description 2
- NPFYZDNDJHZQKY-UHFFFAOYSA-N 4-Hydroxybenzophenone Chemical compound C1=CC(O)=CC=C1C(=O)C1=CC=CC=C1 NPFYZDNDJHZQKY-UHFFFAOYSA-N 0.000 description 2
- ZSBDGXGICLIJGD-UHFFFAOYSA-N 4-phenoxyphenol Chemical compound C1=CC(O)=CC=C1OC1=CC=CC=C1 ZSBDGXGICLIJGD-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 239000004606 Fillers/Extenders Substances 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 description 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 239000012736 aqueous medium Substances 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 239000007859 condensation product Substances 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 230000008034 disappearance Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002148 esters Chemical group 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000011094 fiberboard Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 235000019198 oils Nutrition 0.000 description 2
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 239000011120 plywood Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- 238000004809 thin layer chromatography Methods 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 2
- LALXZDGOWVUSQF-UHFFFAOYSA-N 1-(1-hydroxy-4-nonyl-7-oxabicyclo[4.1.0]hepta-2,4-dien-6-yl)ethanone Chemical compound C1=CC(CCCCCCCCC)=CC2(C(C)=O)OC21O LALXZDGOWVUSQF-UHFFFAOYSA-N 0.000 description 1
- XRUGBBIQLIVCSI-UHFFFAOYSA-N 2,3,4-trimethylphenol Chemical compound CC1=CC=C(O)C(C)=C1C XRUGBBIQLIVCSI-UHFFFAOYSA-N 0.000 description 1
- AQFCDVGUEQOTAC-UHFFFAOYSA-N 2,5-diethylphenol Chemical compound CCC1=CC=C(CC)C(O)=C1 AQFCDVGUEQOTAC-UHFFFAOYSA-N 0.000 description 1
- CROPCLKVTSNPEY-UHFFFAOYSA-N 2-(N-hydroxy-C-phenylcarbonimidoyl)-4-nonylphenol Chemical compound CCCCCCCCCC1=CC=C(O)C(C(=NO)C=2C=CC=CC=2)=C1 CROPCLKVTSNPEY-UHFFFAOYSA-N 0.000 description 1
- ZWJHFFKODHFICU-UHFFFAOYSA-N 2-(hydroxyiminomethyl)-6-methylphenol Chemical compound CC1=CC=CC(C=NO)=C1O ZWJHFFKODHFICU-UHFFFAOYSA-N 0.000 description 1
- GCFSQXQKEFZDBZ-UHFFFAOYSA-N 2-(hydroxyiminomethyl)benzene-1,3-diol Chemical compound ON=CC1=C(O)C=CC=C1O GCFSQXQKEFZDBZ-UHFFFAOYSA-N 0.000 description 1
- GTEXIOINCJRBIO-UHFFFAOYSA-N 2-[2-(dimethylamino)ethoxy]-n,n-dimethylethanamine Chemical compound CN(C)CCOCCN(C)C GTEXIOINCJRBIO-UHFFFAOYSA-N 0.000 description 1
- MKFXLOAJVWVPGD-UHFFFAOYSA-N 2-[N-hydroxy-C-(2-hydroxyphenyl)carbonimidoyl]phenol Chemical compound C=1C=CC=C(O)C=1C(=NO)C1=CC=CC=C1O MKFXLOAJVWVPGD-UHFFFAOYSA-N 0.000 description 1
- HRUHVKFKXJGKBQ-UHFFFAOYSA-N 3,5-dibutylphenol Chemical compound CCCCC1=CC(O)=CC(CCCC)=C1 HRUHVKFKXJGKBQ-UHFFFAOYSA-N 0.000 description 1
- UBOIJEBHNSZRID-UHFFFAOYSA-N 3,5-dicyclohexylphenol 4-octylphenol Chemical compound C1(CCCCC1)C=1C=C(C=C(C1)C1CCCCC1)O.C(CCCCCCC)C1=CC=C(C=C1)O UBOIJEBHNSZRID-UHFFFAOYSA-N 0.000 description 1
- LGGLKPFTYFIQSY-UHFFFAOYSA-N 3-(benzenesulfonyl)thiophene Chemical compound C=1C=CC=CC=1S(=O)(=O)C=1C=CSC=1 LGGLKPFTYFIQSY-UHFFFAOYSA-N 0.000 description 1
- AQIIVEISJBBUCR-UHFFFAOYSA-N 4-(3-phenylpropyl)pyridine Chemical compound C=1C=NC=CC=1CCCC1=CC=CC=C1 AQIIVEISJBBUCR-UHFFFAOYSA-N 0.000 description 1
- RJJVVYVLHWMYAA-UHFFFAOYSA-N 4-(hydroxyiminomethyl)-2-methoxyphenol Chemical compound COC1=CC(C=NO)=CC=C1O RJJVVYVLHWMYAA-UHFFFAOYSA-N 0.000 description 1
- LKVFCSWBKOVHAH-UHFFFAOYSA-N 4-Ethoxyphenol Chemical compound CCOC1=CC=C(O)C=C1 LKVFCSWBKOVHAH-UHFFFAOYSA-N 0.000 description 1
- CHQPRDVSUIJJNP-NSCUHMNNSA-N 4-[(e)-but-2-enyl]phenol Chemical compound C\C=C\CC1=CC=C(O)C=C1 CHQPRDVSUIJJNP-NSCUHMNNSA-N 0.000 description 1
- OAHMVZYHIJQTQC-UHFFFAOYSA-N 4-cyclohexylphenol Chemical compound C1=CC(O)=CC=C1C1CCCCC1 OAHMVZYHIJQTQC-UHFFFAOYSA-N 0.000 description 1
- ILASIIGKRFKNQC-UHFFFAOYSA-N 4-methoxy-3-methylphenol Chemical compound COC1=CC=C(O)C=C1C ILASIIGKRFKNQC-UHFFFAOYSA-N 0.000 description 1
- CYYZDBDROVLTJU-UHFFFAOYSA-N 4-n-Butylphenol Chemical compound CCCCC1=CC=C(O)C=C1 CYYZDBDROVLTJU-UHFFFAOYSA-N 0.000 description 1
- ZNPSUQQXTRRSBM-UHFFFAOYSA-N 4-n-Pentylphenol Chemical compound CCCCCC1=CC=C(O)C=C1 ZNPSUQQXTRRSBM-UHFFFAOYSA-N 0.000 description 1
- OGRAOKJKVGDSFR-UHFFFAOYSA-N 6-Oxy-pseudocumol Natural products CC1=CC(C)=C(C)C(O)=C1 OGRAOKJKVGDSFR-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 229920002522 Wood fibre Polymers 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- YXVFYQXJAXKLAK-UHFFFAOYSA-N biphenyl-4-ol Chemical compound C1=CC(O)=CC=C1C1=CC=CC=C1 YXVFYQXJAXKLAK-UHFFFAOYSA-N 0.000 description 1
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 1
- 235000013877 carbamide Nutrition 0.000 description 1
- 150000001718 carbodiimides Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007596 consolidation process Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- JXCHMDATRWUOAP-UHFFFAOYSA-N diisocyanatomethylbenzene Chemical compound O=C=NC(N=C=O)C1=CC=CC=C1 JXCHMDATRWUOAP-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- SLGWESQGEUXWJQ-UHFFFAOYSA-N formaldehyde;phenol Chemical compound O=C.OC1=CC=CC=C1 SLGWESQGEUXWJQ-UHFFFAOYSA-N 0.000 description 1
- DYDNPESBYVVLBO-UHFFFAOYSA-N formanilide Chemical compound O=CNC1=CC=CC=C1 DYDNPESBYVVLBO-UHFFFAOYSA-N 0.000 description 1
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 1
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 231100000206 health hazard Toxicity 0.000 description 1
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 1
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 235000021388 linseed oil Nutrition 0.000 description 1
- 239000000944 linseed oil Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- DAZXVJBJRMWXJP-UHFFFAOYSA-N n,n-dimethylethylamine Chemical compound CCN(C)C DAZXVJBJRMWXJP-UHFFFAOYSA-N 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- 125000005474 octanoate group Chemical group 0.000 description 1
- 150000005677 organic carbonates Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 239000010690 paraffinic oil Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- ODGAOXROABLFNM-UHFFFAOYSA-N polynoxylin Chemical compound O=C.NC(N)=O ODGAOXROABLFNM-UHFFFAOYSA-N 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 235000000346 sugar Nutrition 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 239000012855 volatile organic compound Substances 0.000 description 1
- 239000002025 wood fiber Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27N—MANUFACTURE BY DRY PROCESSES OF ARTICLES, WITH OR WITHOUT ORGANIC BINDING AGENTS, MADE FROM PARTICLES OR FIBRES CONSISTING OF WOOD OR OTHER LIGNOCELLULOSIC OR LIKE ORGANIC MATERIAL
- B27N3/00—Manufacture of substantially flat articles, e.g. boards, from particles or fibres
- B27N3/002—Manufacture of substantially flat articles, e.g. boards, from particles or fibres characterised by the type of binder
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L97/00—Compositions of lignin-containing materials
- C08L97/02—Lignocellulosic material, e.g. wood, straw or bagasse
Definitions
- This invention relates to a process for the production of wood composite materials.
- This process consists of combining wood particles with a composition, and molding or compressing the combination formed.
- Suitable compositions comprise a blocked polyisocyanate and an aqueous solution of phenolic resin.
- Composite materials such as oriented stand board, particle board and flake board are generally produced by blending or spraying lignocellulose materials such as wood flakes, wood fibers, wood particles, wood wafers, strips or strands, pieces of wood or other comminuted lignocellulose materials with a binder composition while the materials are tumbled or agitated in a blender or like apparatus. After blending sufficiently to form a uniform mixture, the materials are formed into a loose mat, which is compressed between heated platens or plates to set the binder and bond the flakes, strands, strips, pieces, etc., together in densified form. Conventional processes are generally carried out at temperatures of from about 120 to 225° C.
- the moisture content of the lignocellulose material be between about 2 and about 20% by weight, before it is blended with the binder.
- Plywood production is accomplished by roll coating, knife coating, curtain coating, or spraying a binder composition onto veneer surfaces.
- a plurality of veneers are then laid-up to form sheets of required thickness.
- the mats or sheets are then placed in a heated press and compressed to effect consolidation and curing of the materials into a board.
- Binder compositions which have been used in making such composite wood products include phenol formaldehyde resins, urea formaldehyde resins and isocyanates. See, for example, James B. Wilson's paper entitled, “Isocyanate Adhesives as Binders for Composition Board” which was presented at the symposium “Wood Adhesives—Research, Applications and Needs” held in Madison, Wis. on Sep. 23-25, 1980, in which the advantages and disadvantages of each of these different types of binders are discussed.
- Phenolformaldehyde and urea-formaldehyde binders are relatively inexpensive and provide lignocellulosic composites with properties suitable for many application areas. They can be formulated so that emissions of formaldehyde are negligible. Phenol-formaldehyde resins and urea-formaldehyde resins are typically supplied in aqueous media giving them ease of application. They typically have to be used with lignocellulosic materials having lower moisture contents. Otherwise, they demand high temperature and long pressing times to provide cured lignocellulosic composites. They provide boards with high structural strength but may have high water absorption limiting the areas where they can be used.
- Isocyanate binders are commercially desirable because they have flexibility in formulation, versatility with respect to cure temperature and rate, the ability to bond with lignocellulosic materials having high water contents, low water absorption, high adhesive and cohesive strength, excellent structural properties, and no formaldehyde emissions.
- the disadvantages of isocyanates are difficulty in processing due to their high reactivity, adhesion to platens, lack of cold tack, high cost and the need for special storage.
- U.S. Pat. No. 3,870,665 and German Offenlegungsschrift No. 2,109,686 disclose the use of polyisocyanates (and catalysts therefor) in the manufacture of plywood, fiberboard, compression molded articles, as well as various technical advantages when used as binders.
- polymeric MDI polymethylene poly(phenyl isocyanates)
- polymeric MDI polymethylene poly(phenyl isocyanates)
- such treatment involves applying the isocyanate to the material and allowing the isocyanate to cure, either by application of heat and pressure (see, e.g., U.S. Pat. Nos. 3,666,593, 5,008,359, 5,140,086, 5,143,768, and 5,204,176) or at room temperature (see, e.g., U.S. Pat. Nos. 4,617,223 and 5,332,458). While it is possible to allow the polymeric MDI to cure under ambient conditions, residual isocyanate groups remain on the treated products for weeks or even months in some instances. It is also known to utilize toluylene diisocyanate for such purposes.
- Isocyanate prepolymers are among the preferred isocyanate materials which have been used in binder compositions to solve various processing problems, particularly adhesion to press platens and high reactivity.
- U.S. Pat. No. 4,100,328 discloses isocyanate-terminated prepolymers which improve product release from a mold.
- U.S. Pat. No. 4,609,513 also discloses a process in which an isocyanate-terminated prepolymer binder is used to improve product release.
- a binder composition in which a particular type of isocyanate prepolymer is used to improve adhesiveness at room temperature is disclosed in U.S. Pat. No. 5,179,143.
- a major processing difficulty encountered with isocyanate binders is the rapid reaction of the isocyanate with water present in the lignocellulosic material and any water present in the binder composition itself.
- One method for minimizing this difficulty is to use only lignocellulosic materials having a low moisture content (i.e., a moisture content of from about 3 to about 8%). This low moisture content is generally achieved by drying the cellulosic raw material to reduce the moisture content. Such drying is, however, expensive and has a significant effect upon the economics of the process.
- Use of materials having low moisture contents is also disadvantageous because panels made from the dried composite material tend to absorb moisture and swell when used in humid environments.
- This prepolymer is prepared by reacting (1) about 0.05 to about 0.5 hydroxyl equivalents of a polyol having a functionality of from 2 to 8 and a molecular weight of from about 62 to about 2000 with (2) one equivalent of a polyisocyanate mixture containing (a) from 0 to about 50% by weight of polyphenyl polymethylene polyisocyanate and (b) about 50 to about 100% by weight isomer mixture of diphenylmethane diisocyanate containing 10 to 75% by weight of 2,4′-isomer and 25 to 90% by weight of 4,4′-isomer.
- U.S. Pat. No. 4,944,823 describes a composition for bonding solid lignocellulosic materials.
- Suitable binder formulations are based on the reactive mixture of an isocyanate and a carbohydrate material. These are both effective and inexpensive, and eliminate health hazards associated with the use of formaldehyde.
- Carbohydrate materials include, for example, sugars and starches, in the presence or absence of other active materials. These carbohydrates are mixed with a liquid diisocyanate and applied to the wood, which is then pressed to form a composite product.
- Binder compositions comprising phenolic resins and polyisocyanates are known and described in, for example, U.S. Pat. Nos. 3,905,934, 4,293,480, 4,602,069, 4,683,252, 5,001,190, 5,101,001 and 5,733,952, and WO 88/03090 and WO 89/07626. These binder compositions are disclosed as being suitable for foundry cores and molds. The materials are typically applied in an organic solvent and cured most often in the presence of gaseous amine vapors.
- U.S. Pat. No. 5,001,190 and PCT application WO 88/03090 disclose a process for filling a space within a structure with a polyurethane composite in the presence of water.
- Suitable polyurethane composites comprise (a) adding a coarse aggregate to the space in the structure to be filled, (b) adding a polyurethane binder to the aggregate, wherein the binder comprises (i) a phenolic resin component comprising a resole phenolic resin and a hydrophobic solvent system, and (ii) a polyisocyanate component comprising an aromatic polyisocyanate and a hydrophobic solvent, and (iii) a urethane promoting catalyst.
- compositions of U.S. Pat. No. 5,733,952 also comprise an epoxy resin and, preferably, paraffinic oil. Polymerized linseed oil is utilized in the binders of WO 89/07626.
- Isocyanates are known to be suitable components for treating cellulosic fiber and wood products. Some processes for this treatment are described in, for example, U.S. Pat. Nos. 5,179,143 and 5,674,568.
- the binders of U.S. Pat. No. 5,179,143 comprise polyisocyanates, compounds containing at least two isocyanate reactive hydrogen atoms and alkylene carbonates.
- 5,674,568 comprise a polymethylene poly(phenylisocyanate), water, and an organic compound having a hydroxy functionality of from 2 to 8 and a molecular weight of about 60 to 8000 and being selected from the group consisting of ester group-free polyhydric alcohols, polyether polyols and mixtures thereof.
- Binders comprising polyisocyanates and phenolic resins are known and described as being suitable for preparing wood composite products by U.S. Pat. Nos. 4,209,433, and 5,217,665. Suitable phenolic resins disclosed by these references are resole resins. U.S. Pat. No. 4,209,433 requires that the polyisocyanate be added to the wood particles prior to the application of the phenolic resin, thereby producing enhanced adhesive characteristics.
- the binder compositions of U.S. Pat. No. 4,961,795 may be cured with a curing agent comprising an ester, a lactone or an organic carbonate, which may be moderated by an aliphatic mono- or polyhydric alcohol.
- a method of producing waferboard is described by U.S. Pat. No. 5,217,665. This method comprises applying first a liquid phenol formaldehyde resin to the surface of the wafers, then a powdered phenol formaldehyde resin. This is followed by forming layup and pressing at elevated temperature and pressure using steam pressing techniques to consolidate the layup into a board and to set the phenolic resin adhesive.
- a disadvantage common to these patents is that the polyisocyanate and resole resin must be added separately. Mixtures of the aqueous phenolic with unmodified organic polyisocyanates are often incompatible and unstable. The mixtures separate quickly and the isocyanate forms insoluble ureas upon reaction with the aqueous solvent. This reaction is accelerated by the base present in most resoles.
- a solution to the problems of limited potlife stability is to block the isocyanate groups.
- a method to improve compatibility is to incorporate groups that make the polyisocyanate water dispersible.
- use of water dispersible blocked polyisocyanates may avoid disadvantages of prior art combinations of polyisocyanate and aqueous phenolic resins.
- Water dispersible polyisocyanate is typically blocked prior to dispersing it in water as described in U.S. Pat. Nos. 4,522,851, 4,098,933, and 4,284,544.
- the disadvantage of blocking the polyisocyanate before it is dispersed in water is that the blocked polyisocyanate is generally a solid or a high viscosity liquid which is very difficult or impossible to disperse in water without first diluting the blocked polyisocyanate in an organic solvent or heating the blocked polyisocyanate to an elevated temperature to reduce its viscosity.
- unique blocking agents that contain both oxime and phenol functionality, it is possible to form the blocked polyisocyanate in aqueous solution avoiding highly viscous intermediates.
- the blocking agent is not volatilized as the composite is pressed, but rather it is incorporated into the binder by reaction with the phenolic resin.
- the present invention relates to a process for the production of wood composite materials comprising a) combining wood particles with 2 to 15% by weight, based on the total weight of the wood composite, of a composition, and b) molding or compressing the combination formed in a).
- the compression or molding typically occurs at pressures of from about 200 to 1000 psi (preferably 300 to 700 psi) for about 2 to 10 (preferably 4 to 8) minutes at temperatures of from about 120° C. to 220° C. (preferably 150 to 200° C.).
- compositions for this invention consist essentially of
- an aqueous dispersion of a blocked polyisocyanate component consisting essentially of an adduct of:
- a polymethylene poly(phenylisocyanate) having a functionality of about 2.1 to about 3.5, an NCO group content of from about 30% to about 33%, and a monomer content of from about 30% to about 90% by weight, wherein the content of the monomer comprises from up to about 5% by weight of the 2,2′-isomer, from about 1% to about 20% by weight of the 2,4′-isomer, and from about 25% to about 65% by weight of the 4,4′-isomer, based on the entire weight of the polyisocyanate; and
- R represents a hydrogen atom, an alkyl group having from 1 to 12 carbon atom, a phenyl group, or a substituted phenyl group, and preferably represents a substituted hydroxyphenyl group;
- X represents a hydrogen atom, an alkyl group having from 1 to 12 carbon atoms, an alkoxy group having from 1 to 12 carbon atoms, a phenyl group, a substituted phenyl group, or a methylol radical, and preferably an alkyl methylol radical;
- weight ratio of component (1) to component (2) is from 4:1 to 1:20, preferably from 1:1 to 1:10, most preferably from 1:2 to 1:5, and wherein the weight ratio of component (1 )(i) to (1 )(ii) is from 10:1 to 1:10, preferably from 5:1 to 1:5 and most preferably from 2:1 to 1:1.
- wood particles are combined with from about 2 to 15% by weight, preferably from 4 to 10% by weight, most preferably with from 5 to 8% by weight of the binder compositions, based on the total weight of the wood composite.
- the solids content of the sum of (1) the dispersion of the blocked polyisocyanate and (2) the aqueous solution of the resole is from 10 to 70%, (i.e., water is 30 to 90%), preferably from 20 to 60% (i.e., water is 40 to 80%), and most preferably from 30 to 55% (i.e., water is 45-70%), based on the combined weight of (1) and (2).
- the binders When the binders are combined in this ratio, they are aqueous solutions or aqueous dispersions with potlifes extended compared to those prepared from the aqueous resole and unmodified polymeric MDI.
- the aqueous dispersion of the blocked polyisocyanate component, i.e., component (1), of the present invention consists essentially of an adduct of (i) a polymethylene poly(phenylisocyanate) component and (ii) a compound corresponding to one of the specified structures below. It is preferably formed in the presence of component (2), the aqueous solution of the phenolic resin.
- Polymeric MDI refers to the three-ring and/or higher ring products derived by the phosgenation of aniline-formaldehyde condensation products.
- Suitable polyisocyanates to be used as component (1)(i) of the compositions in the present invention include those polymethylene poly(phenylisocyanate) blends having an NCO group content of about 25% to 33% by weight, and having a viscosity of less than about 2,000 cps at 25° C.
- the polyisocyanates of the present invention have a functionality of from about 2.1 to about 3.5, preferably 2.3 to 3.0 and most preferably of 2.6 to 2.8, and an NCO group content of about 30% to about 33%, preferably about 30.5% to about 32.5%, and a monomer content of from about 30% to about 90% by weight, preferably from about 40% to about 70%, wherein the content of monomer comprises up to about 5% by weight of the 2,2′-isomer, from about 1 to about 20% by weight of the 2,4′-isomer, and from about 25 to about 65% by weight of the 4,4′-isomer, based on the entire weight of the blend.
- the polymeric MDI content of these isocyanates varies from about 10 to about 70% by weight, preferably from about 30% to about 60% by weight.
- the polyisocyanates used as component (1)(i) in the present invention have an average functionality of about 2.3 to about 3.0, most preferably of about 2.4 to about 2.8, and a monomer content of preferably 40 to 80%, most preferably of 40 to 70% by weight.
- the content of monomeric MDI preferably comprises less than 1% by weight of the 2,2′-isomer of MDI, less than 5% by weight of the 2,4′-isomer of MDI and from about 30 to about 60% by weight of the 4,4′-isomer of MDI, based on the entire weight of the polyisocyanate.
- Preferred polyisocyanates have viscosities of 10 to 1000 cps, more preferred polyisocyanates have viscosities of 40 to 400, and most preferred polyisocyanates have viscosities of 100 to 300 cps.
- a preferred polymethylene poly(phenylisocyanate) blend has a functionality of from 2.2 to 2.4, an NCO group content of from about 31.2 to about 32.8% by weight, and a monomer content of from about 55% to about 80%, wherein the content of monomer comprises no more than about 3% by weight of the 2,2′-isomer, from about 15% to about 20% by weight of the 2,4′-isomer and from about 40% to about 55% by weight of the 4,4′-isomer, based on the entire weight of the blend.
- This polyiso-cyanate blend comprises from about 20 to about 45% by weight of polymeric MDI.
- Most preferred polyisocyanates include, for example, polymethylene poly(phenylisocyanate) blends having an average functionality of from about 2.5 to about 3.0, preferably about 2.6 to about 2.8, an NCO group content of about 30 to 32% by weight, and a monomer content of from about 40 to 50% by weight, wherein the content of monomer comprises no more than about 1 % by weight of the 2,2′-isomer, from about 2 to about 10% by weight of the 2,4′-isomer and from about 35 to about 45% by weight of the 4,4′-isomer, based on the entire weight of the blend.
- This isocyanate blend comprises from about 50 to about 60% by weight of polymeric MDI.
- Suitable polyisocyanates for component (1)(i) of the present invention also include, for example, mixtures of polyisocyanate blends as described above with adducts of MDI including, for example, allophanates of MDI as described in, for example, U.S. Pat. Nos. 5,319,053, 5,319,054 and 5,440,003, the disclosures of which are herein incorporated by reference, and carbodiimides of MDI as described in, for example, U.S. Pat. Nos. 2,853,473, 2,941,966, 3,152,162, 4,088,665, 4,294,719 and 4,244,855, the disclosures of which are herein incorporated by reference. Modified polyisocyanates are less preferred.
- Suitable compounds to be used as blocking agents, i.e. component (1 )(ii), for the polymethylene poly(phenyl isocyanates) of the present invention include, for example, those compounds corresponding to the general formulas below:
- R represents a hydrogen atom, an alkyl group having from 1 to 12 carbon atoms, a phenyl group, or a substituted phenyl group; and preferably a substituted hydroxyphenyl group;
- X represents a hydrogen atom, an alkyl group having from 1 to 12 carbon atoms, an alkoxy group having from 1 to 12 carbon atoms, a phenyl group, a substituted phenyl group, or a methylol radical, preferably an alkyl methylol radical, and most preferably an alkyl methylol radical having from 1 to 12 carbon atoms.
- suitable compounds for blocking the polyisocyanate include but are not limited to compounds such as 2-hydroxybenzaldoxime, 3-hydroxybenzaldoxime, 4-hydroxybenzaldoxime, 2,6-dihydroxybenzaldoxime, heptylsalicylaldoxime, octylsalicylaldoxime, nonylsalicylaldoxime, dodecylsalicylaldoxime, 2-hydroxy-3-methyl benzaldoxime, 4-hydroxy-3-methoxybenzaldoxime, 2′-hydroxy-5′-nonylacetophenone oxide, 2′-hydroxy-5′-nonyl benzophenone oxime, 2,2′-dihydroxybenzophenone oxime, 4,4′-dihydroxybenzophenone oxime, etc.
- Preferred compounds are 2-hydroxybenzaldoxime, 3-hydroxybenzaldoxime, 4-hydroxybenzaldoxime, heptylsalicylaldoxime, octylsalicylaldoxime, nonylsalicylaldoxime, dodecylsalicylaldoxime, and 4,4′-dihydroxybenzophenone oxime.
- the weight ratio of the isocyanate in the polymethylene poly(phenylisocyanate) (1 )(i) to the blocking agent (1)(ii) can be from about 10:1 to about 1:10, preferably from about 5:1 to about 1:5, and most preferably from about 2:1 to about 1:1.
- the blocked polyisocyanates can be and preferably are prepared directly in an aqueous solution.
- a base neutralized solution of the blocking agent can be added to the polyisocyanate.
- the isocyanate is added to the base neutralized solution of the blocking agent.
- the isocyanate is added to a mixture of the base neutralized aqueous solution and the resole resin.
- a neutralizing agent must be present for the phenolic group in an amount such that from 10 to 100%, preferably from 50 to 100%, most preferably from 70 to 100% of the molar amount of the phenolic groups are neutralized.
- suitable bases to be used as neutralizing agents in the present invention include compounds such as sodium hydroxide, potassium hydroxide, ammonia, amines, especially tertiary amines, and trimethyl ethanolamine.
- Sodium hydroxide is a particularly preferred neutralizing agent.
- Phenolic resins are obtained by the condensation of a phenolic compound with an aldehyde.
- Resole and resitole resins are prepared generally using an alkaline catalyst with excess formaldehyde and result in polymers having pendant methylol groups.
- the resins are characterized by high viscosity. Since each methylol group constitutes a potential cross-linking site, the resole and resitole resins are readily converted to the cross-linked, infusible polymers by heating. However, these resins can be highly unstable.
- Suitable phenolic resins for the present invention are present as aqueous solutions with pH of 8-13 and are classified as resole resins.
- the solids levels of these resoles are typically in the range of 10 to 70%, based on the weight of the resin plus water in the solutions. They are prepared using an excess of aldehyde in alkaline catalyzed reaction with phenols.
- Suitable examples of such resole resins are known and described in, for example, U.S. Pat. Nos. 3,839,251 and 4,961,795, the disclosures of which are herein incorporated by reference. Additional information relative to the preparation of the phenolic resins can be found in, for example, the Encyclopedia of Chemical Technology by Kirk Othmer, Fourth Edition, Volume 18, pp. 609-612.
- Suitable phenolic resins for the present invention compositions are
- R represents a hydrogen atom or a phenolic substituent meta to the phenolic hydroxyl group
- R represents a hydrogen atom or another hydroxyl group substituent meta to the phenolic group
- X represents an end group from the group consisting of hydrogen, methylol, and alkyl methylol, wherein the molar ratio of methylol and alkyl methylol to hydrogen end groups is greater than 1:1;
- n and n are each independently selected from a number between 0 and 20.
- resole resins are typically prepared by the reaction of a suitable phenol group containing compound wherein an excess of the aldehyde group containing compound is present.
- suitable phenolic components include nonyl phenol, as well as virtually any of the phenols which are not substituted at either the two ortho-positions or at one ortho and the para-positions. It is necessary that these positions be unsubstituted for the polymerization reaction with the aldehyde to occur. Any one, all, or none of the remaining carbon atoms of the phenol ring can be substituted.
- substituted phenols employed in the formation of the resole resins include, for example, alkyl-substituted phenols, aryl-substituted phenols, cyclo-alkyl-substituted phenols, alkenyl-substituted phenols, alkoxy-substituted phenols, aryloxy-substituted phenols, and halogen-substituted phenols, the foregoing substituents containing from 1 to 26 and preferably from 1 to 12 carbon atoms.
- Suitable phenols include, for example, phenol, 2,6-xylenol, o-cresol, m-cresol, p-cresol, 3,5-xylenol, 3,4-xylenol, 2,3,4-trimethyl phenol, 3-ethyl phenol, 2,5-diethyl phenol, p-butyl phenol, 3,5-dibutyl phenol, p-amyl phenol, p-cyclohexyl phenol, p-octyl phenol 3,5-dicyclohexyl phenol, p-phenyl phenol, p-crotyl phenol, 3,5-dimethoxy phenol, 3,4,5-trimethoxy phenol, p-ethoxy phenol, p-butoxy phenol, 3-methyl-4-methoxy phenol, and p-phenoxy phenol.
- Such phenols can be described by the formula:
- A, B, and C each independently represents a hydrogen atom, a hydroxyl radical, a hydrocarbon radical, an oxyhydrocarbon radical or a halogen radical.
- suitable phenolic compounds are those compounds containing a second phenolic group such as, for example, catechol, resorcinol and hydroquinone.
- the aldehydes reacted with the phenol can include any of the aldehydes theretofore employed in the formation of phenolic resins such as, for example, formaldehyde, acetaldehyde, propionaldehyde, furfuraldehyde, and benzaldehyde.
- the aldehydes employed have the formula: R′CHO wherein R′ is a hydrogen or a hydrocarbon radical of 1 to 8 carbon atoms.
- Formaldehyde is the most preferred aldehyde.
- Suitable catalysts for accelerating the isocyanate addition reaction with hydroxyls may in principle be used in forming these binder compositions.
- the use of catalysts is not, however, necessary to the present invention.
- Suitable catalysts for this purpose include, for example, tin compounds such as dibutyl tin dilaurate or tin(ll) octoate; and tertiary amines such as, for example, triethylene diamine, dimethylethyl amine, pyridine, 4-phenylpropyl pyridine, bis(N,N-dimethylaminoethyl)ether, N,N′-dimethylaminoethyl-N-methyl ethanolamine, N,N-dimethylaminoethyl morpholine, quinoline, morpholine, N-methyl morpholine, etc.
- catalysts are described in “Kunstoff Handbuch”, Volume VII, published by Becker and Braun, Carl Hanser Verlag, Kunststoff, 1983 on pages 92-98.
- the catalysts are used, if at all, in a quantity of about 0.001 to 10% by weight, preferably about 0.002 to 0.1% by weight, based on the total quantity of reactants.
- surface active additives e.g., emulsifiers and stabilizers
- mold release agents such as, for example, zinc stearate, etc.
- stabilizing agents which reduce swelling and water absorption there may be mentioned sodium chloride, sodium sulfate, paraffin, fatty acids or their salts such as zinc stearate and other similar materials. At the same time, paraffin and fatty acids and their salts may serve as release agents. Use of other active materials may shorten pressing and curing time.
- the percentages of ingredients in the wood binder compositions according to the present invention can vary widely according to needs and conditions of a particular application. In general, however, quantities in the defined ranges have been found suitable, bearing in mind that the other active materials may comprise one or more of the catalysts, stabilizing agents and release agents.
- This binder formulation may be used in an amount of 2 to 15% by weight, based on the resin solids expressed as a percentage of the total wood weight.
- the quantity of solid binder formulation based on the weight of the wood is about 4 to 10%, most preferably 5-8%, depending on the configuration of the particulate wood and the requirements of the products.
- Binder formulations according to the present invention are made by blending together the various components in the proper sequence as noted above.
- such blending preferably involves vigorous agitation for several minutes, such as in a suitable mill, reactor, or other mixing device, in order to insure thorough blending of the isocyanate with the other components. It is preferable to blend together first the phenolic resin with the blocking agent, catalyst and release agent (if one or more of these latter components are used) and then to add the polyisocyanate.
- the blending should be carried out for a time sufficient to produce a homogeneous blend, and under vigorous blending conditions, this will usually occur after several minutes of vigorous agitation.
- the solids level of the binder formulation can be in the range of 10 to 70%, based on the weight of the solid binder plus water. It is preferred that the solids level be 20 to 60% and most preferably 35 to 55%.
- the binder formulations are applied to wood particles in the manufacture of particle board, wafer board, fiber board, etc., by intermixing a stream of wood particles with a stream of the aqueous binder formulation at the desired ratio and using mechanical agitation which is common in the manufacture of composite products such as particle board.
- the wood may have a wide range of moisture content, i.e., from about 1 to about 15% by weight, based on the total weight of the wood particles.
- it is advantageous if the moisture content of the wood particles is relatively low, i.e., on the order of about 2 to 8%.
- the binder and resultant products are free of formaldehyde and volatile blocking agents.
- the resulting products have property levels that are improved compared to those prepared using the phenolic resin alone.
- Isocyanate A a polymethylene poly(phenylisocyanate) blend having a viscosity of 200 mPa ⁇ s, and an isocyanate content of 31.5%.
- Resole A an aqueous solution of phenol formaldehyde resin prepared using excess formaldehyde. It has solids level about 57.5%, a viscosity of about 190 mPa ⁇ s, and a pH value of about 11; commercially available from Borden Chemical under the name Cascophen® OS707.
- Blocking Agent A 4-hydroxybenzaldehyde oxime (This component was prepared in the laboratory by the following procedure.)
- Blocking Agent B 3-hydroxybenzaldehyde oxime (This compound was prepared in the laboratory using the procedure as described above for Blocking Agent A, except that the 4-hydroxybenzaldehyde starting material was replaced with the isomer 3-hydroxybenzaldehyde.) The resultant product was a dark tan oil, which crystallized upon standing neat (no water).
- Blocking Agent C bis (4-hydroxy) benzophenone oxime (This compound was prepared in the laboratory by the following procedure.)
- Blocking Agent A Into a 300 ml beaker, 9.45 g (68.9 mmol) of Blocking Agent A and 100 g of distilled water were added. Then, 5.50 g (68.75 mmol) of sodium hydroxide solution (50% aqueous) were added while stirring. 90.59 g (689.9 mmol) of Isocyanate A were added over a period of 10 minutes to the oxime sample while being mixed under high shear (4000-5000 rpm). The mixture was discharged into 822 g of Resole A, which was being stirred at 3000-4000 rpm. The resin mixture was stirred for an additional 5 minutes until it appeared to be homogeneous. The resin mixture was stored at 4° C. for 16 h prior to evaluation in oriented strandboard panels.
- Blocking Agent B Into a 300 ml beaker, 40.00 g (291.69 mmol) of Blocking Agent B and 85 g of distilled water were added. 23.33 g (291.62 mmol) of sodium hydroxide solution (50% aqueous) were added while stirring. 38.29 g (291.62 mmol) of Isocyanate A were added over a period of 10 minutes to the oxime sample while being mixed under high shear (4000-5000 rpm). The mixture was discharged into 680 g of Resole A, which was being stirred at 3000-4000 rpm. The resin mixture was stirred for an additional 5 minutes until it appeared to be homogeneous. The resin mixture was stored at 4° C. for 16 h prior to evaluation in oriented strandboard panels.
- the aspen strands used were obtained from the Louisiana-Pacific Corporation of Portland, Oreg. They had moisture contents in the range of from 1% to 10%.
- the average strand size was targeted to be 0.03′′ ⁇ 0.5′′ ⁇ 1.75′′ (thickness/width/length).
- MOR Modulus of Rupture
- a 6-cycle test was used to evaluate the delamination and strength retention of specimens of the product after six moisture cycles. This test was conducted as follows. The specimen size was 2′′ ⁇ 14′′ and each specimen was weathered per APA Test Method D-5 which is described as follows:
- a control particleboard specimen was prepared using the procedure described above, with the exception that Resole A was substituted for Binder D.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Materials Engineering (AREA)
- Forests & Forestry (AREA)
- Manufacturing & Machinery (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Dry Formation Of Fiberboard And The Like (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
Description
TABLE 1 |
Results of Binder A-C samples in laboratory prepared oriented strandboard. |
Density | IB | MOR | Six cycle | 6-MOR | % Water | % Thickness | ||
Example | Description | (Pcf) | (psi) | (psi) | MOR | % Retention | Absorption | Swell |
1 | Binder A | 40.24 | 43.3 | 3351 | 1296 | 38.9 | 36.3 | 13.6 |
2 | Binder B | 40.00 | 34.8 | 3074 | 1488 | 49.6 | 38.1 | 14.0 |
3 | Binder C | 39.96 | 30.7 | 2370 | 1323 | 54.7 | 35.9 | 15.3 |
4 (Control) | Resole A | 39.93 | 44.1 | 3088 | 1836 | 64.7 | 31.1 | 9.1 |
TABLE 2 |
Results of Binder D sample analysis in |
laboratory prepared particleboard. |
Density | |||||
Density (IB) | IB | (swell) | Thickness | ||
Example | Description | (lb./cu. Ft.) | (psi) | (lb./cu. ft.) | Swell, % |
5 (Control) | Resole A | 41 | 21 | 43 | 35 |
6 | Binder D | 44 | 43 | 42 | 37 |
Claims (16)
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US09/465,279 US6416696B1 (en) | 1999-12-16 | 1999-12-16 | Aqueous mixed pMDI/phenolic resin binders for the production of wood composite products |
CA002327677A CA2327677C (en) | 1999-12-16 | 2000-12-06 | Aqueous mixed pmdi/phenolic resin binders for the production of wood composite products |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US09/465,279 US6416696B1 (en) | 1999-12-16 | 1999-12-16 | Aqueous mixed pMDI/phenolic resin binders for the production of wood composite products |
Publications (1)
Publication Number | Publication Date |
---|---|
US6416696B1 true US6416696B1 (en) | 2002-07-09 |
Family
ID=23847140
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US09/465,279 Expired - Lifetime US6416696B1 (en) | 1999-12-16 | 1999-12-16 | Aqueous mixed pMDI/phenolic resin binders for the production of wood composite products |
Country Status (2)
Country | Link |
---|---|
US (1) | US6416696B1 (en) |
CA (1) | CA2327677C (en) |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20050051921A1 (en) * | 2003-09-05 | 2005-03-10 | Weyerhaeuser Company | Process for making engineered lignocellulosic-based panels |
US20050054807A1 (en) * | 2003-09-05 | 2005-03-10 | Weyerhaeuser Company | Low-nitrogen content phenol-formaldehyde resin |
US20050147823A1 (en) * | 2003-12-29 | 2005-07-07 | Mark Oliver | Treatment of porous filler materials for use with resins |
US20050242459A1 (en) * | 2004-04-29 | 2005-11-03 | Savino Thomas G | Lignocellulosic composite material and method for preparing the same |
US20060128886A1 (en) * | 2004-12-14 | 2006-06-15 | Winterowd Jack G | Low-nitrogen content phenol-formaldehyde resin |
US20110151180A1 (en) * | 2008-08-13 | 2011-06-23 | Haupt Robert A | Rapid curing aldehyde resin-polyisocyanate composition and method for producing hybrid polymer |
WO2018023095A1 (en) * | 2016-07-29 | 2018-02-01 | Georgia-Pacific Chemicals Llc | Processes for making composite products with binders containing blocked isocyanates |
US10889716B2 (en) * | 2016-05-26 | 2021-01-12 | Georgia-Pacific Chemicals Llc | Binders containing an aldehyde-based resin and an isocyanate-based resin and methods for making composite lignocellulose products therefrom |
US11780112B2 (en) | 2016-05-26 | 2023-10-10 | Bakelite Chemicals Llc | Binders containing an aldehyde-based resin and an isocyanate-based resin and methods for making composite lignocellulose products therefrom |
Citations (37)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3438940A (en) | 1965-04-03 | 1969-04-15 | Bayer Ag | Process of preparing water dispersible polyurethanes and resulting product |
US3666593A (en) | 1969-10-27 | 1972-05-30 | Us Plywood Champ Papers Inc | Process for making a polyisocyanate-impregnated,paper-overlaid panel |
US3870665A (en) | 1973-05-22 | 1975-03-11 | Bayer Ag | Process for making pressure molded lignocellulose articles comprising isocyanurate group forming mold release agent |
GB1387454A (en) | 1971-03-02 | 1975-03-19 | Bayer Ag | Process for the production of materials having properties which contain lignocellulose |
US3905934A (en) | 1974-05-23 | 1975-09-16 | Ashland Oil Inc | Phenolic resin-polyisocyanate binder systems containing dialkyl phthalate solvents |
US4098933A (en) | 1974-11-29 | 1978-07-04 | Bayer Aktiengesellschaft | Process for the production of water-soluble or water-dispersible blocked polyisocyanates |
US4100328A (en) | 1976-06-04 | 1978-07-11 | Basf Wyandotte Corporation | Binder composition and process for preparing pressure molded cellulosic articles |
US4209433A (en) | 1978-12-19 | 1980-06-24 | The United States Of America As Represented By The Secretary Of Agriculture | Method of bonding particle board and the like using polyisocyanate/phenolic adhesive |
US4284544A (en) | 1978-12-14 | 1981-08-18 | Bayer Aktiengesellschaft | Process for the preparation of water-dispersible or water-soluble blocked polyisocyanates, the blocked polyisocyanates obtainable by this process and lacquer binders containing these blocked polyisocyanates as isocyanate component |
US4293480A (en) | 1979-05-11 | 1981-10-06 | Ashland Oil, Inc. | Urethane binder compositions for no-bake and cold box foundry application utilizing isocyanato-urethane polymers |
US4522851A (en) | 1982-09-30 | 1985-06-11 | Mobay Chemical Corporation | Process for coating aqueous dispersion of epoxy resin and blocked polyisocyanate containing chemically incorporated anionic hydrophilic groups |
US4546039A (en) | 1982-05-03 | 1985-10-08 | Basf Aktiengesellschaft | Process for bonding lignocellulose-containing raw materials with a prepolymer based on a urethane-modified diphenylmethane diisocyanate mixture |
US4602069A (en) | 1984-04-11 | 1986-07-22 | Ashland Oil, Inc. | Phenolic resin-polyisocyanate binder systems containing a phosphorus based acid |
US4609513A (en) | 1984-08-15 | 1986-09-02 | Jim Walter Research Corp. | Binder composition for manufacture of fiberboard |
US4617223A (en) | 1984-11-13 | 1986-10-14 | The Mead Corporation | Reinforced paperboard cartons and method for making same |
US4683252A (en) | 1986-02-25 | 1987-07-28 | Ashland Oil, Inc. | Phenolic resin-polyisocyanate binder systems containing an organohalophosphate and use thereof |
WO1988003090A1 (en) | 1986-10-28 | 1988-05-05 | Ashland Oil, Inc. | Polyurethane composites comprising a coarse aggregate and certain polyurethane binders |
WO1989007626A1 (en) | 1988-02-16 | 1989-08-24 | Ashland Oil, Inc. | Low solids polyurethane-forming foundry binders for cold-box process |
US4944823A (en) | 1985-09-26 | 1990-07-31 | Carbocol, Inc. | Composition for bonding solid lignocellulosic materials |
US4961795A (en) | 1986-09-03 | 1990-10-09 | Borden, Inc. | Composition and process for bonding lignocellulosic material |
US5001190A (en) | 1986-10-28 | 1991-03-19 | Ashland Oil, Inc. | Process for filling space in a structure with a polyurethane composite in the presence of water |
US5008359A (en) | 1988-11-25 | 1991-04-16 | Weyerhaeuser Company | Isocyanate modified cellulose products and method for their manufacture |
US5101001A (en) | 1989-12-21 | 1992-03-31 | Ashland Oil, Inc. | Polyurethane-forming foundry binders and their use |
US5130419A (en) * | 1990-03-09 | 1992-07-14 | Imperial Chemical Industrial Plc | Process for preparing lignocellulosic bodies |
US5140086A (en) | 1988-11-25 | 1992-08-18 | Weyerhaeuser Company | Isocyanate modified cellulose products and method for their manufacture |
US5143768A (en) | 1991-08-30 | 1992-09-01 | Weyerhaeuser Company | Laminated dieboard structure |
US5179143A (en) | 1988-07-26 | 1993-01-12 | Bayer Aktiengesellschaft | Process for the preparation of compression molded materials |
US5204176A (en) | 1992-03-03 | 1993-04-20 | The Dow Chemical Company | Structural siding composition |
US5217665A (en) | 1992-02-25 | 1993-06-08 | Borden Inc. | Phenol formaldehyde steam pressing of waferboard |
US5296160A (en) | 1991-07-23 | 1994-03-22 | Miles Inc. | Aqueous dispersions of blocked polyisocyanates |
US5332458A (en) | 1991-04-29 | 1994-07-26 | Weyerhaeuser Co | Corrugated paperboard strength enhancing process |
US5674568A (en) | 1995-10-03 | 1997-10-07 | Bayer Corporation | Treatment of cellulosic fiber products |
US5733952A (en) | 1995-10-18 | 1998-03-31 | Borden Chemical, Inc. | Foundry binder of phenolic resole resin, polyisocyanate and epoxy resin |
US5750201A (en) * | 1995-04-13 | 1998-05-12 | Imperial Chemical Industries Plc | Process for binding lignocellulosic material |
WO2000035985A1 (en) | 1998-12-17 | 2000-06-22 | Bayer Corporation | Process for production of wood composites using a mixed pmdi/solid novolac resin binder |
US6096805A (en) | 1996-10-29 | 2000-08-01 | Huels Aktiengesellschaft | Stable and high solids aqueous dispersions of blocked polyisocyanates |
US6214265B1 (en) * | 1998-12-17 | 2001-04-10 | Bayer Corporation | Mixed PMDI/resole resin binders for the production of wood composite products |
-
1999
- 1999-12-16 US US09/465,279 patent/US6416696B1/en not_active Expired - Lifetime
-
2000
- 2000-12-06 CA CA002327677A patent/CA2327677C/en not_active Expired - Fee Related
Patent Citations (37)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3438940A (en) | 1965-04-03 | 1969-04-15 | Bayer Ag | Process of preparing water dispersible polyurethanes and resulting product |
US3666593A (en) | 1969-10-27 | 1972-05-30 | Us Plywood Champ Papers Inc | Process for making a polyisocyanate-impregnated,paper-overlaid panel |
GB1387454A (en) | 1971-03-02 | 1975-03-19 | Bayer Ag | Process for the production of materials having properties which contain lignocellulose |
US3870665A (en) | 1973-05-22 | 1975-03-11 | Bayer Ag | Process for making pressure molded lignocellulose articles comprising isocyanurate group forming mold release agent |
US3905934A (en) | 1974-05-23 | 1975-09-16 | Ashland Oil Inc | Phenolic resin-polyisocyanate binder systems containing dialkyl phthalate solvents |
US4098933A (en) | 1974-11-29 | 1978-07-04 | Bayer Aktiengesellschaft | Process for the production of water-soluble or water-dispersible blocked polyisocyanates |
US4100328A (en) | 1976-06-04 | 1978-07-11 | Basf Wyandotte Corporation | Binder composition and process for preparing pressure molded cellulosic articles |
US4284544A (en) | 1978-12-14 | 1981-08-18 | Bayer Aktiengesellschaft | Process for the preparation of water-dispersible or water-soluble blocked polyisocyanates, the blocked polyisocyanates obtainable by this process and lacquer binders containing these blocked polyisocyanates as isocyanate component |
US4209433A (en) | 1978-12-19 | 1980-06-24 | The United States Of America As Represented By The Secretary Of Agriculture | Method of bonding particle board and the like using polyisocyanate/phenolic adhesive |
US4293480A (en) | 1979-05-11 | 1981-10-06 | Ashland Oil, Inc. | Urethane binder compositions for no-bake and cold box foundry application utilizing isocyanato-urethane polymers |
US4546039A (en) | 1982-05-03 | 1985-10-08 | Basf Aktiengesellschaft | Process for bonding lignocellulose-containing raw materials with a prepolymer based on a urethane-modified diphenylmethane diisocyanate mixture |
US4522851A (en) | 1982-09-30 | 1985-06-11 | Mobay Chemical Corporation | Process for coating aqueous dispersion of epoxy resin and blocked polyisocyanate containing chemically incorporated anionic hydrophilic groups |
US4602069A (en) | 1984-04-11 | 1986-07-22 | Ashland Oil, Inc. | Phenolic resin-polyisocyanate binder systems containing a phosphorus based acid |
US4609513A (en) | 1984-08-15 | 1986-09-02 | Jim Walter Research Corp. | Binder composition for manufacture of fiberboard |
US4617223A (en) | 1984-11-13 | 1986-10-14 | The Mead Corporation | Reinforced paperboard cartons and method for making same |
US4944823A (en) | 1985-09-26 | 1990-07-31 | Carbocol, Inc. | Composition for bonding solid lignocellulosic materials |
US4683252A (en) | 1986-02-25 | 1987-07-28 | Ashland Oil, Inc. | Phenolic resin-polyisocyanate binder systems containing an organohalophosphate and use thereof |
US4961795A (en) | 1986-09-03 | 1990-10-09 | Borden, Inc. | Composition and process for bonding lignocellulosic material |
US5001190A (en) | 1986-10-28 | 1991-03-19 | Ashland Oil, Inc. | Process for filling space in a structure with a polyurethane composite in the presence of water |
WO1988003090A1 (en) | 1986-10-28 | 1988-05-05 | Ashland Oil, Inc. | Polyurethane composites comprising a coarse aggregate and certain polyurethane binders |
WO1989007626A1 (en) | 1988-02-16 | 1989-08-24 | Ashland Oil, Inc. | Low solids polyurethane-forming foundry binders for cold-box process |
US5179143A (en) | 1988-07-26 | 1993-01-12 | Bayer Aktiengesellschaft | Process for the preparation of compression molded materials |
US5008359A (en) | 1988-11-25 | 1991-04-16 | Weyerhaeuser Company | Isocyanate modified cellulose products and method for their manufacture |
US5140086A (en) | 1988-11-25 | 1992-08-18 | Weyerhaeuser Company | Isocyanate modified cellulose products and method for their manufacture |
US5101001A (en) | 1989-12-21 | 1992-03-31 | Ashland Oil, Inc. | Polyurethane-forming foundry binders and their use |
US5130419A (en) * | 1990-03-09 | 1992-07-14 | Imperial Chemical Industrial Plc | Process for preparing lignocellulosic bodies |
US5332458A (en) | 1991-04-29 | 1994-07-26 | Weyerhaeuser Co | Corrugated paperboard strength enhancing process |
US5296160A (en) | 1991-07-23 | 1994-03-22 | Miles Inc. | Aqueous dispersions of blocked polyisocyanates |
US5143768A (en) | 1991-08-30 | 1992-09-01 | Weyerhaeuser Company | Laminated dieboard structure |
US5217665A (en) | 1992-02-25 | 1993-06-08 | Borden Inc. | Phenol formaldehyde steam pressing of waferboard |
US5204176A (en) | 1992-03-03 | 1993-04-20 | The Dow Chemical Company | Structural siding composition |
US5750201A (en) * | 1995-04-13 | 1998-05-12 | Imperial Chemical Industries Plc | Process for binding lignocellulosic material |
US5674568A (en) | 1995-10-03 | 1997-10-07 | Bayer Corporation | Treatment of cellulosic fiber products |
US5733952A (en) | 1995-10-18 | 1998-03-31 | Borden Chemical, Inc. | Foundry binder of phenolic resole resin, polyisocyanate and epoxy resin |
US6096805A (en) | 1996-10-29 | 2000-08-01 | Huels Aktiengesellschaft | Stable and high solids aqueous dispersions of blocked polyisocyanates |
WO2000035985A1 (en) | 1998-12-17 | 2000-06-22 | Bayer Corporation | Process for production of wood composites using a mixed pmdi/solid novolac resin binder |
US6214265B1 (en) * | 1998-12-17 | 2001-04-10 | Bayer Corporation | Mixed PMDI/resole resin binders for the production of wood composite products |
Non-Patent Citations (1)
Title |
---|
James B. Wilson's paper entitled, "Isocyanate Adhesives as Binders for Composition Board" which was presented at the symposium "Wood Adhesives-Research, Applications and Needs" head in Madison, Wisconsin on Sep. 23-25, 1980. |
Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20050051921A1 (en) * | 2003-09-05 | 2005-03-10 | Weyerhaeuser Company | Process for making engineered lignocellulosic-based panels |
US20050054807A1 (en) * | 2003-09-05 | 2005-03-10 | Weyerhaeuser Company | Low-nitrogen content phenol-formaldehyde resin |
US7141195B2 (en) | 2003-09-05 | 2006-11-28 | Weyerhaeuser Co. | Process for making engineered lignocellulosic-based panels |
US20050147823A1 (en) * | 2003-12-29 | 2005-07-07 | Mark Oliver | Treatment of porous filler materials for use with resins |
US20050242459A1 (en) * | 2004-04-29 | 2005-11-03 | Savino Thomas G | Lignocellulosic composite material and method for preparing the same |
US20080119590A1 (en) * | 2004-04-29 | 2008-05-22 | Basf Corporation | Lignocellulosic composite material and method for preparing the same |
US20060128886A1 (en) * | 2004-12-14 | 2006-06-15 | Winterowd Jack G | Low-nitrogen content phenol-formaldehyde resin |
US20110151180A1 (en) * | 2008-08-13 | 2011-06-23 | Haupt Robert A | Rapid curing aldehyde resin-polyisocyanate composition and method for producing hybrid polymer |
US8865287B2 (en) | 2008-08-13 | 2014-10-21 | Robert A. Haupt | Rapid curing aldehyde resin-polyisocyanate composition and method for producing hybrid polymer |
US10889716B2 (en) * | 2016-05-26 | 2021-01-12 | Georgia-Pacific Chemicals Llc | Binders containing an aldehyde-based resin and an isocyanate-based resin and methods for making composite lignocellulose products therefrom |
US11780112B2 (en) | 2016-05-26 | 2023-10-10 | Bakelite Chemicals Llc | Binders containing an aldehyde-based resin and an isocyanate-based resin and methods for making composite lignocellulose products therefrom |
WO2018023095A1 (en) * | 2016-07-29 | 2018-02-01 | Georgia-Pacific Chemicals Llc | Processes for making composite products with binders containing blocked isocyanates |
Also Published As
Publication number | Publication date |
---|---|
CA2327677C (en) | 2009-02-17 |
CA2327677A1 (en) | 2001-06-16 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US6641761B2 (en) | Mixed PMDI/resole resin binders for the production of wood composite products | |
US6641762B2 (en) | Mixed PMDI/solid novolac resin binders for the production of wood composite products | |
US6635695B2 (en) | Adhesive composition for lignocellulose-type hot-pressed forms, and hot-pressed form production process using the same | |
KR102005769B1 (en) | Wood adhesive formulation | |
KR102005768B1 (en) | Wood adhesive composition | |
JP2002532293A (en) | Extended polymethylene poly (phenylisocyanate) resin binder for the manufacture of wood composite products | |
JP2002533249A (en) | Method for producing wood composite material containing thixotropic binder composition | |
KR102005767B1 (en) | Wood adhesive formulation | |
US6416696B1 (en) | Aqueous mixed pMDI/phenolic resin binders for the production of wood composite products | |
EP1345978B1 (en) | Aqueous mixed pmdi/phenolic resin binders for the production of wood composite products | |
JP4632165B2 (en) | Adhesive composition for lignocellulosic hot-press molded body and method for producing hot-press molded body using the same | |
JP4697645B2 (en) | Adhesive composition for lignocellulosic hot-press molded body and method for producing hot-press molded body using the same | |
JP2003082323A (en) | Adhesive composition for lignocellulose-based hot-press molded article, and method for manufacturing hot-press molded article using the same | |
MXPA01006020A (en) | Process for production of wood composites using a mixed pmdi/solid novolac resin binder |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: BAYER CORPORATION, PENNSYLVANIA Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:MILLER, TODD R.;ROSTHAUSER, JAMES W.;REEL/FRAME:010698/0298;SIGNING DATES FROM 20000207 TO 20000221 Owner name: BORDEN CHEMICAL INC., OREGON Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:MILLER, TODD R.;ROSTHAUSER, JAMES W.;REEL/FRAME:010698/0298;SIGNING DATES FROM 20000207 TO 20000221 |
|
STCF | Information on status: patent grant |
Free format text: PATENTED CASE |
|
AS | Assignment |
Owner name: FLEET CAPITAL CORPORATION, AS AGENT, ILLINOIS Free format text: SECURITY INTEREST;ASSIGNOR:BORDEN CHEMICAL, INC.;REEL/FRAME:013288/0937 Effective date: 20020923 Owner name: FLEET NATIONAL BANK, LONDON U.K. BRANCH, TRADING A Free format text: SECURITY INTEREST;ASSIGNOR:BORDEN CHEMICAL, INC.;REEL/FRAME:013288/0937 Effective date: 20020923 Owner name: FLLET CAPITAL CANADA CORPORATION, AS CANADIAN AGEN Free format text: SECURITY INTEREST;ASSIGNOR:BORDEN CHEMICAL, INC.;REEL/FRAME:013288/0937 Effective date: 20020923 |
|
AS | Assignment |
Owner name: WILMINGTON TRUST COMPANY, AS COLLATERAL AGENT, DEL Free format text: SECURITY AGREEMENT;ASSIGNORS:RESOLUTION PERFORMANCE PRODUCTS LLC;RESOLUTION SPECIALTY MATERIALS LLC;BORDEN CHEMICAL, INC.;REEL/FRAME:016522/0428 Effective date: 20050831 Owner name: JPMORGAN CHASE BANK, N.A., AS ADMINISTRATIVE AGENT Free format text: SECURITY AGREEMENT;ASSIGNORS:RESOLUTION PERFORMANCE PRODUCTS LLC;RESOLUTION SPECIALTY MATERIALS LLC;BORDEN CHEMICAL, INC.;REEL/FRAME:016480/0648 Effective date: 20050831 |
|
FPAY | Fee payment |
Year of fee payment: 4 |
|
AS | Assignment |
Owner name: WILMINGTON TRUST COMPANY, AS COLLATERAL AGENT,DELA Free format text: SECURITY AGREEMENT;ASSIGNOR:HEXION SPECIALTY CHEMICALS, INC.;REEL/FRAME:018535/0701 Effective date: 20061103 Owner name: WILMINGTON TRUST COMPANY, AS COLLATERAL AGENT, DEL Free format text: SECURITY AGREEMENT;ASSIGNOR:HEXION SPECIALTY CHEMICALS, INC.;REEL/FRAME:018535/0701 Effective date: 20061103 Owner name: JPMORGAN CHASE BANK, N.A. AS ADMINISTRATIVE AGENT, Free format text: SECURITY AGREEMENT;ASSIGNOR:HEXION SPECIALTY CHEMICALS, INC.;REEL/FRAME:018535/0556 Effective date: 20061103 |
|
FPAY | Fee payment |
Year of fee payment: 8 |
|
AS | Assignment |
Owner name: WILMINGTON TRUST FSB, AS COLLATERAL AGENT,MINNESOT Free format text: SECURITY INTEREST;ASSIGNORS:HEXION SPECIALTY CHEMICALS, INC.;BORDEN CHEMICAL FOUNDRY, LLC;BORDEN CHEMICAL INVESTMENTS, INC.;AND OTHERS;REEL/FRAME:023963/0038 Effective date: 20100129 Owner name: WILMINGTON TRUST FSB, AS COLLATERAL AGENT, MINNESO Free format text: SECURITY INTEREST;ASSIGNORS:HEXION SPECIALTY CHEMICALS, INC.;BORDEN CHEMICAL FOUNDRY, LLC;BORDEN CHEMICAL INVESTMENTS, INC.;AND OTHERS;REEL/FRAME:023963/0038 Effective date: 20100129 |
|
AS | Assignment |
Owner name: JPMORGAN CHASE BANK, N.A., AS ADMINISTRATIVE AGENT Free format text: SECURITY AGREEMENT;ASSIGNORS:HEXION LLC;HEXION SPECIALTY CHEMICALS, INC.;BORDEN CHEMICAL FOUNDRY, LLC;AND OTHERS;REEL/FRAME:023905/0451 Effective date: 20100129 |
|
AS | Assignment |
Owner name: BORDEN CHEMICAL, INC. NKA HEXION SPECIALTY CHEMICA Free format text: RELEASE BY SECURED PARTY;ASSIGNORS:FLEET CAPITAL CORPORATION AS AGENT;FLEET CAPITAL CANADA CORPORATION, AS CANADIAN AGENT;FLEET NATIONAL BANK, LONDON U.K. BRANCH TA/FLEETBOSTON FINANCIAL, AS UK AGENT;REEL/FRAME:024785/0369 Effective date: 20100610 |
|
FPAY | Fee payment |
Year of fee payment: 12 |
|
AS | Assignment |
Owner name: BAYER MATERIALSCIENCE LLC, PENNSYLVANIA Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:BAYER CORPORATION;REEL/FRAME:035064/0270 Effective date: 20141231 |
|
AS | Assignment |
Owner name: COVESTRO LLC, PENNSYLVANIA Free format text: CHANGE OF NAME;ASSIGNOR:BAYER MATERIALSCIENCE LLC;REEL/FRAME:036876/0585 Effective date: 20150901 |
|
AS | Assignment |
Owner name: HEXION INC., OHIO Free format text: RELEASE BY SECURED PARTY;ASSIGNOR:WILMINGTON TRUST COMPANY;REEL/FRAME:039360/0724 Effective date: 20160630 |
|
AS | Assignment |
Owner name: HEXION INC. (FORMERLY KNOWN AS HEXION SPECIALTY CH Free format text: RELEASE BY SECURED PARTY;ASSIGNOR:WILMINGTON TRUST, NATIONAL ASSOCIATION (SUCCESSOR BY MERGER TO WILMINGTON TRUST FSB), AS COLLATERAL AGENT;REEL/FRAME:041793/0001 Effective date: 20170208 Owner name: HEXION INTERNATIONAL INC. (FORMERLY KNOWN AS BORDE Free format text: RELEASE BY SECURED PARTY;ASSIGNOR:WILMINGTON TRUST, NATIONAL ASSOCIATION (SUCCESSOR BY MERGER TO WILMINGTON TRUST FSB), AS COLLATERAL AGENT;REEL/FRAME:041793/0001 Effective date: 20170208 Owner name: LAWTER INTERNATIONAL INC., OHIO Free format text: RELEASE BY SECURED PARTY;ASSIGNOR:WILMINGTON TRUST, NATIONAL ASSOCIATION (SUCCESSOR BY MERGER TO WILMINGTON TRUST FSB), AS COLLATERAL AGENT;REEL/FRAME:041793/0001 Effective date: 20170208 Owner name: BORDEN CHEMICAL FOUNDRY, LLC, OHIO Free format text: RELEASE BY SECURED PARTY;ASSIGNOR:WILMINGTON TRUST, NATIONAL ASSOCIATION (SUCCESSOR BY MERGER TO WILMINGTON TRUST FSB), AS COLLATERAL AGENT;REEL/FRAME:041793/0001 Effective date: 20170208 Owner name: HEXION INVESTMENTS INC. (FORMERLY KNOWN AS BORDEN Free format text: RELEASE BY SECURED PARTY;ASSIGNOR:WILMINGTON TRUST, NATIONAL ASSOCIATION (SUCCESSOR BY MERGER TO WILMINGTON TRUST FSB), AS COLLATERAL AGENT;REEL/FRAME:041793/0001 Effective date: 20170208 Owner name: HSC CAPITAL CORPORATION, OHIO Free format text: RELEASE BY SECURED PARTY;ASSIGNOR:WILMINGTON TRUST, NATIONAL ASSOCIATION (SUCCESSOR BY MERGER TO WILMINGTON TRUST FSB), AS COLLATERAL AGENT;REEL/FRAME:041793/0001 Effective date: 20170208 Owner name: HEXION CI HOLDING COMPANY (CHINA) LLC, DISTRICT OF Free format text: RELEASE BY SECURED PARTY;ASSIGNOR:WILMINGTON TRUST, NATIONAL ASSOCIATION (SUCCESSOR BY MERGER TO WILMINGTON TRUST FSB), AS COLLATERAL AGENT;REEL/FRAME:041793/0001 Effective date: 20170208 Owner name: OILFIELD TECHNOLOGY GROUP, INC., OHIO Free format text: RELEASE BY SECURED PARTY;ASSIGNOR:WILMINGTON TRUST, NATIONAL ASSOCIATION (SUCCESSOR BY MERGER TO WILMINGTON TRUST FSB), AS COLLATERAL AGENT;REEL/FRAME:041793/0001 Effective date: 20170208 Owner name: HEXION U.S. FINANCE CORP., OHIO Free format text: RELEASE BY SECURED PARTY;ASSIGNOR:WILMINGTON TRUST, NATIONAL ASSOCIATION (SUCCESSOR BY MERGER TO WILMINGTON TRUST FSB), AS COLLATERAL AGENT;REEL/FRAME:041793/0001 Effective date: 20170208 |